Coating composition, method for coating a surface of a material using the same, and surface treated materials having the same

ABSTRACT

A coating composition, a method for coating a surface of a material using the same, and surface treated materials having the same are provided. The coating composition comprises a nitrogen atom-containing organopolysiloxane represented by the average siloxane unit formula (1): (R 1 R 2 R 3 SiO 1/2 ) a (SiR 1   2 O 2/2 ) b (R 2 R 3 SiO 2/2 ) c (R 2 R 3   2 SiO 1/2 ) d  (1) wherein R 1  is a nitrogen-free, substituted or unsubstituted, monovalent organic group of 1 to 20 carbon atoms, R 2  is a monovalent organic group containing at least one nitrogen atom, R 3  is an organoxy group represented by —OR 1 , “a” is a positive number of 0.7 to 1.3; “b” is a positive number of 2 to 500; “c” is a positive number of 0 to 10; “d” is a positive number 0.7 to 1.3: and a+d is at least 2.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a U.S. national stage filing under 35 U.S.C. §371 ofPCT Application No. PCT/CN2012/079159 filed on Jul. 26, 2012, currentlypending which claims the benefit of Chinese Patent Application No.20110221874.6 filed Jul. 29, 2011 under 35 U.S.C. §119 (a)-(d) and 35U.S.C. §365(a). PCT Application No. PCT/CN2012/079159 and Chinese PatentApplication No. 201110221874.6 are hereby incorporated by reference.

TECHNICAL FIELD

The present invention relates to a coating composition, a method forcoating a surface of a material using the same, and surface treatedmaterials having the same.

BACKGROUND OF THE INVENTION

Prior art literatures such as U.S. Pat. Nos. 5,391,675, 5,118,535 and6,515,095 disclose nitrogen atom-containing polysiloxanes and suchpolysiloxanes can be used for textile treatment. However, suchpolysiloxanes impart insufficient properties (for example, anti-tapeproperty, solvent resistance and anti-ink property) as a coatingcomposition.

SUMMARY

The present invention provides a novel coating composition which impartssufficient properties as a coating composition, thus overcoming thedefects in the prior art.

In one aspect, the present invention provides a coating compositioncontaining a nitrogen atom-containing organopolysiloxane represented bythe average siloxane unit formula (1):(R¹R²R³SiO_(1/2))_(a)(SiR¹ ₂O_(2/2))_(b)(R²R³SiO_(2/2))_(c)(R²R³₂SiO_(1/2))_(d)   (1)wherein R¹ is a nitrogen-free, substituted or unsubstituted, monovalentorganic group of 1 to 20 carbon atoms, R² is a monovalent organic groupcontaining at least one nitrogen atom, R³ is an organoxy grouprepresented by —OR¹, “a” is a positive number of 0.7 to 1.3; “b” is apositive number of 2 to 500; “c” is a positive number of 0 to 10; “d” isa positive number 0.7 to 1.3: and a+d is at least 2.

In a preferred embodiment, the coating composition further comprises anorganic polymer binder.

In another preferred embodiment, R² is a following general formula (2):—R⁴(NR⁵CH₂CH₂) _(e)NR⁶ ₂   (2)wherein, R⁴ is a divalent hydrocarbon group of 1 to 6 carbon atoms, R⁵and R⁶ are independently selected from hydrogen and unsubstituted orhydroxyl-substituted monovalent hydrocarbon groups of 1 to 50 carbonatoms which may be separated by an oxygen atom, and. “e” is an integerof 0 to 4.

In another preferred embodiment, R² is —C₃H₆NH₂—C₃H₆NHC₂H₄NH₂ or—C₃H₆NHC₂H₄NHC₂H₄NH₂.

In another preferred embodiment, R³ is OCH₃ or OC₂H₅.

In another preferred embodiment, “c” is 0.

In another preferred embodiment, “b” is a number of 5 to 100.

In another preferred embodiment, the organic polymer binder is selectedfrom the group comprising acrylic resin, polyurethane resin, epoxyresin, alkyd resin, polyamid resin, and the mixture of at least two ofthem.

In another preferred embodiment, the composition further comprises asolvent.

In another aspect, the present invention provides a method for coating asurface of a material, characterized in that the surface of the materialis coated with the above coating composition.

In still another aspect, the present invention provides surface treatedmaterials with a coating composition

DESCRIPTION OF THE PREFERRED EMBODIMENT (Draft)

<Nitrogen Atom-Containing Organopolysiloxane>

The coating composition of the present invention is characterized bycontaining a nitrogen atom-containing organopolysiloxane represented bythe average siloxane unit formula (1):(R¹R²R³SiO_(1/2))_(a)(SiR¹ ₂O_(2/2))_(b)(R²R³SiO_(2/2))_(c)(R²R³₂SiO_(1/2))_(d)   (1)wherein R¹ is a nitrogen-free, substituted or unsubstituted, monovalentorganic group of 1 to 20 carbon atoms, R² is a monovalent organic groupcontaining at least one nitrogen atom, R³ is an organoxy grouprepresented by —OR¹, “a” is a positive number of 0.7 to 1.3; “b” is apositive number of 0 to 500; “c” is a positive number of 0 to 10; “d” isa positive number 0.7 to 1.3: and a+d is at least 2.

Such organopolysiloxane impart superior properties to a coating surfacewhich made from the composition of the invention, such as anti-tapeproperty, solvent resistance, anti-ink property, and so on. The amountof the nitrogen atom-containing organopolysiloxane in the coatingcomposition or the present invention is preferably in the rage of 0.001to 30 weight %, and more preferably in the range of 0.1 to 10 weight %,based on the total weight of the coating composition as 100 weight %.

In the organopolysiloxanes of the invention, the organic groupsrepresented by le include substituted or unsubstituted monovalenthydrocarbon groups of 1 to 20 carbon atoms, and especially 1 to 3 carbonatoms. Examples of the organic groups represented by R¹ include alkylgroups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl,decyl, dodecyl, tetradecyl, octadecyl, and eicosyl, alkenyl groups suchas vinyl, allyl, propenyl, butenyl and hexenyl, aryl groups such asphenyl and tolyl, aralkyl groups such as benzyl, phenylethyl andphenylpropyl, cycloalkyl groups such as cyclopentyl and cyclohexyl, andsubstituted ones of the foregoing groups in which some or all of thehydrogen atoms attached to carbon atoms are replaced by halogen atoms,e.g., halogenated alkyl groups such as chloromethyl and trifluoropropyl,and halogenated aryl groups such as chlorophenyl. Of these, preferablyat least 90 mol % of the R¹ groups are methyl, phenyl, andtrifluoropropyl.

R² stands for monovalent organic groups containing at least one nitrogenatom, for examples, groups of the following formulae (2) and (3).

R⁴ stands for divalent hydrocarbon groups of 1 to 6 carbon atoms, forexample, alkylene groups such as methylene, dimethylene, trimethylene,tetramethylene, pentamethylene, and hexamethylene. Of these,trimethylene is desirable.

R⁵ and R⁶ are independently hydrogen or unsubstituted orhydroxyl-substituted monovalent hydrocarbon groups of 1 to 50 carbonatoms which may be separated by an oxygen atom, especially unsubstitutedor hydroxyl-substituted alkyl groups. Examples are monovalenthydrocarbon groups of 1 to 8 carbon atoms including alkyl groups such asmethyl, ethyl, propyl, butyl, pentyl, hexyl and octyl, and phenyl. Alsoincluded are groups represented by COR wherein R is an alkyl group of 1to 10 carbon atoms and groups represented byCH₂CH(OH)CH₂O(C₂H₄O)_(n)R⁹wherein R⁹ is hydrogen or a monovalent hydrocarbon group such as C 1-8alkyl, and n is a positive number of 0 to 10. R⁵ and R⁶ may be the sameor different, and a pair of R⁶ may also be the same or different. Ofthese groups, hydrogen and methyl are preferred.

R⁷ is —CH═, —N═, —OCH═, or —ON═, and R⁸ is hydrogen or methyl.

In formula (2), “e” is an integer of 0 to 4. Illustrative examples ofthe organic group R² represented by formula (2) include—C₃H₆NH₂,—C₃H₆NHC₂H₄NH₂, and—C₃H₆NHC₂H₄NHC₂H₄NH₂.

Also included are substituted ones of these illustrative examples inwhich one or two hydrogen atoms in NH or NH₂ are replaced by COR whereinR is a C1-10 alkyl group and in which one or two hydrogen atoms in NH orNH₂ are replaced by CH₂CH(OH)CH₂O(C₂H₄O)_(n)R⁹ wherein R⁹ is hydrogen ora monovalent hydrocarbon group (e.g., C1-8 alkyl) and n is a positivenumber of 0 to 10.

In formula (1), R³ is an organoxy group represented by —OR¹, preferablyan alkoxy group of 1 to 6 carbon atoms. Illustrative examples of R³ aremethoxy, ethoxy and propoxy groups, with methoxy being most preferred.

Letter “a” is a positive number of 0.7 to 1.3, preferably 1. Letter “d”is a positive number 0.7 to 1.3, preferably 1. “a”+“d” is at least 2,and is preferably is 2.

Letter “b” is a positive number of 2 to 500, and preferably 5 to 100,more preferably 40.

Letter “c” is a positive number of 0 to 10, and preferably 0.

<Synthesis of the Nitrogen-Containing Organoplolysiloxane>

The nitrogen atom-containing polyorganosiloxane of the invention can beprepared by effecting alcohol-removing reaction among a (i)diorganopolysiloxane of which both terminals of the molecular chain arecapped with hydroxydiorganosilyl group represented by the followingaverage structural formula:(R¹ ₂(HO)SiO_(1/2))₁(SiR¹ ₂O_(2/2))_(f)(R¹ ₂(HO)SiO_(1/2))₁;(ii) a dialkoxysilane having a nitrogen atom-containing organic grouprepresented by the following formula:R¹R²Si(OR³)₂;(iii) and a trialkoxysilane having a nitrogen atom-containing organicgroup represented by the following formula:R²Si(OR³)₃wherein R¹, R², and R³ are similar to mentioned above. And “f” is apositive number of 0 to 498, and preferably 3 to 98

Preferable reaction temperature might be in the range from roomtemperature to 150 degree C., more preferably in the range from roomtemperature to 100 degree C.

By this reaction, a nitrogen atom-containing polysiloxane as representedby formula (1) is readily obtained. Since the alcohol by-productprecludes the progress of reaction, reaction must be effected under anitrogen stream while removing the resultant alcohol. No solvent isgenerally necessary although a solvent such as toluene or xylene may beused if the component (i) has a high viscosity. If the reaction is slow,a catalyst such as triethylamine or tetramethylene ethylenediamine isoptionally used.

The molar ratio of the component (i) to the component (ii) ((i)/(ii)) ispreferably in the range of 0.7 to 1.3, and more preferably in the rangeof 0.8 to 1.2.

The molar ratio of the component (i) to the component (iii) ((i)/(iii))is preferably in the range of 0.7 to 1.3, and more preferably in therange of 0.8 to 1.2.

And the molar ratio of the component (ii) to the component (iii)((ii)/(iii)) is preferably in the range of 0.7 to 1.3, and morepreferably in the range of 0.8 to 1.2.

<Coating Composition>

The coating composition of the present invention contains thenitrogen-containing organoplolysiloxane. And the composition may takethe form of solutions of the polysiloxane in organic solvents such astoluene, xylene, n-hexane, n-heptane, methyl ethyl ketone, methylisobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, celluloseacetate-butyl, diethyl ether, isopropyl ether, n-buthyl ether,tetrahydrofuran, dimethyl carbonate, ehylmethyl carbonate, and mineralturpentine, or emulsions of the polysiloxane with the aid of nonionic,anionic, cationic or ampholytic surfactants.

<Organic Polymer Binder>

The composition preferably further comprises an organic polymer binder.Preferred organic polymer binders include polyurethanes, phenolicresins, epoxy resins, acrylic resins, acrylic-modified polyolefinresins, polyester resins, amino-formaldehyde resins, vinyl resins, forexample polyvinyl butyral, acryl-urethane resin, alkyd resin, urearesins, amino resins, amino alkyd resins, fluoric resins, andpolyamideimide resins. Preferred polyurethanes include copolymers of apolyester or polyether polyol and an aromatic or aliphatic diisocyanate.The level of organic polymer binder can for example be in the range 0.2or 0.3% up to 90% by weight of the coating composition. Levels oforganic polymer binder of for example 5% up to 80% by weight of thecoating composition are often preferred.

<Other Components>

To the composition of the invention, suitable additives may be addedinsofar as the advantages of the composition are not impaired. Suchadditives are silicon compounds such as dimethylpoly-siloxane, alpha,omega-dihydroxydimethylpolysiloxane, silicone resins, andalkoxy-silanes, and other additives such as inorganic fillers, organicfillers, hollow particles, pigments, dyes, anti-foaming agents, levelingagents, thickeners, anti-blocking agents, UV absorvers, anti-creasingagents, flame retardants, antistatic agents, antioxidants,preservatives, and anti-rusting agents.

<Preparation of the Coating Composition>

The composition of the invention may be prepared by conventionalwell-known techniques. Usually the nitrogen-atom containingorganopolysiloxane and other ingredients are mixed uniformly with amixer.

<Substrates>

The composition of the invention can apply on the surface of variouskinds of substrates by spraying, dipping, knife-coating, roll-coating,and so on. Preferred substrates include organic fibber, glass fibber,carbon fibber and other kinds of fibbers; paper, textile, non-wovenfabric and other kinds of fibrous substrates; woods, particle boards,plywood, laminated woods, and other kinds of wood-base materials;glasses, metals, concrete and other kinds of inorganic substrates; andplastics.

<Applicable Industrial Use>

The composition of the invention can be preferably used as an interiorand exterior coating for transporting machines, such as automobile,ships and airplane; an interior coating for construction materials, suchas wall papers, floor materials, decorative boards, and furniture; anexterior coatings for electric devices, such as mobile phones, personaldata assistances, and personal computers; and exterior coating forclothes, stationeries, and accessories.

EXAMPLE

Examples of the invention are given below by way of illustration and notby way of limitation.

Synthetic Example 1

744.5 g (0.25 mol) of dimethylpolysiloxane of which both terminals ofthe molecular chain are capped with hidoroxydimethylsilyl grouprepresented by the following average structural formula:HO(CH₃)₂SiO—((CH₃)₂SiO)₃₈—Si(CH₃)₂OH, 48.6 g (0.22 mol) ofaminopropyl-triethoxysilane, and 42.0 g (0.22 mol) ofaminopropyl-methyldiethoxysilane were mixed homogenously and then heatedto 85 degree C. and removing ethanol during the heating. When thegeneration of ethanol stopped, the reaction mixture was cooled down toroom temperature (25 degree C.).

The obtained organopolysiloxane (B-1) was subject to structuralidentification by ²⁹Si-NMR. From the analytical results and the reactionroute, the product was identified to have the following average siloxaneunit formula represented by the formula;(H₂NC₃H₆(CH₃)(C₂H₅O)SiO_(1/2))₁ ((CH₃)₂ SiO_(2/2))₄₀(H₂NC₃H₆(C₂H₅O)₂SiO_(1/2))₁

Synthetic Example 2

387.1 g (0.13 mol) of dimethylpolysiloxane of which both terminals ofthe molecular chain are capped with hidoroxydimethylsilyl grouprepresented by the following average structural formula:HO(CH₃)₂SiO—((CH₃)₂SiO)₃₈—Si(CH₃)₂OH and 42.9 g (0.21 mol) ofaminopropyl-methyldimethoxysilane were mixed homogenously and thenheated to 85 degree C. and removing ethanol during the heating. When thegeneration of ethanol stopped, the reaction mixture was cooled down toroom temperature (25 degree C.).

The obtained organopolysiloxane (B-2) was subject to structuralidentification by ²⁹Si-NMR. From the analytical results and the reactionroute, the product was identified to have the following average siloxaneunit formula represented by the formula;(H₂NC₃H₆(CH₃)(CH₃O)SiO_(1/2))₂ ((CH₃)₂ SiO_(2/2))₄₀

Synthetic Example 3

387.1 g (0.13 mol) of dimethylpolysiloxane of which both terminals ofthe molecular chain are capped with hidoroxydimethylsilyl grouprepresented by the following average structural formula:HO(CH₃)₂SiO—((CH₃)₂SiO)₃₈—Si(CH₃)₂OH and 57.5 g (0.26 mol) ofaminopropyl-triethoxysilane were mixed homogenously and then heated to85 degree C. and removing ethanol during the heating. When thegeneration of ethanol stopped, the reaction mixture was cooled down toroom temperature (25 degree C.). The obtained organopolysiloxane (B-3)was subject to structural identification by ²⁹Si-NMR. From theanalytical results and the reaction route, the product was identified tohave the following average siloxane unit formula represented by theformula;(H₂NC₃H₆(C₂H₅O)₂SiO_(1/2))₂ ((CH₃)₂SiO_(2/2))₄₀

Example 1 and Comparative Example 1-3

Coating compositions are prepared by uniformly mixed ingredients in theproportion of Table 1. The coating compositions were sprayed on thesurface of paper and cured by passing 160 degree C. oven at 80 m/minspeed. After post cure treatment at 65 degree C. for 72 hours, surfacecoated paper test pieces were obtained. The obtained test pieces wereevaluated in anti-tape property, solvenn resistance, and anti-inkproperty. The results are shown in Table 2.

TABLE 1 Acrylic resin 65 Cellulose acetate-butyl 2 Toluene 5 EthylAcetate 16 Cyclohexanone 2 Butyl Acetate 9 Silicone additive 1 (weight%)

TABLE 2 Comparative Comparative Comparative Example 1 Example 1 Example2 Example 3 Silicone B-1 B-2 B-4 B-5 additive Anti-tape more than 15 12more than 15 more than 15 (time) Solvent more than 10  5 8 6 resistanceAnti-ink no spoor stained stained stainedTest Methods:Anti-Tape Property:

Nitto Denko No. 31B tape was put on the coated surface of the testpiece, adhered with a rubber roller and peeled off. Such procedure wasrepeated 15 times. If the coated surface was damaged or the tape couldnot remove from the coated surface during the test, the test wasterminated and number of the procedures was recorded.

Solvent Resistance:

The coated surface of the test piece was wiped with a cloth dipped inbutyl acetate 10 times. If the coated surface was damaged during thetest, the test was terminated and number of wiping was recorded.

Anti-Ink Property:

A few drops of ink was dropped on the coated surface and wiped off witha dry cloth. After wiping off, the coated surface was observed visually.If the ink was completely wiped off, the test result was rated as “nospoor”. If a stain was observed in trace proportions, the test resultwas rated as “stained”.

Here in after, the wording in the tables 1 and 2 are represented;

Acrylic resin: BS-965 acrylic resin; trade name (purchased from JiangsuSanmu Group Corporation)

Silicone Additive

-   -   (B-1): the organopolysiloxane obtained in synthetic example 1    -   (B-2): the organopolysiloxane obtained in synthetic example 2    -   (B-4): an organopolysiloxane represented by the formula:        (CH₃)₃SiO—(Si(CH₃)₂O)₁₀₅—(Si(CH₃)(C₃H₆NHC₂H₂NH₂)O)₂-Si(CH₃)₃    -   (B-5): an organopolysiloxane represented by the formula:        (CH₃)₃SiO—(Si(CH₃)₂O)₈₆—(Si(CH₃)(C₃H₆NH₂)O)₄—Si(CH₃)₃

Comparative Example 4

Coating compositions prepared by the same manner of example 1 exceptsilicone additive (B-3) was used instead of silicone additive (B-1). Thecoating composition was coated on the surface of paper and cured in 160degree C. oven at 80 m/min. However, certain amounts of small bubbleswere observed on the coated surface.

Comparative Example 5

744.5 g (0.25 mol) of dimethylpolysiloxane of which both terminals ofthe molecular chain are capped with hidoroxydimethylsilyl grouprepresented by the following average structural formula:HO(CH₃)₂SiO—((CH₃)₂SiO)₃₈—Si(CH₃)₂OH, 33.2 g (0.15 mol) ofaminopropyl-trithoxysilane, and 42.0 g (0.22 mol) ofaminopropyl-methyldiethoxysilane were mixed homogenously and then heatedto 85 degree C. and removing ethanol during the heating. When thegeneration of ethanol stopped, the reaction mixture was cooled down toroom temperature (25 degree C.).

The obtained organopolysiloxane (B-6) was subject to structuralidentification by ²⁹Si-NMR. From the analytical results and the reactionroute, the product was identified to have the following average siloxaneunit formula represented by the formula;(H₂NC₃H₆(CH₃)(C₂H₅O)SiO_(1/2))_(1.7) ((CH₃)₂ SiO_(2/2))_(83.3)(H₂NC₃H₆(C₂H₅O)SiO_(2/2))_(0.3) (H₂NC₃H₆(C₂H₅O)₂SiO_(1/2))_(0.3)

Using the obtained organopolysiloxane (B-6), a coating composition andtest piece was prepared in the same manner of example 1. Anti-tapeproperties and Solvent resistance of the test pieces were evaluated. Theresults were shown in Table 3.

TABLE 3 Comparative Example 5 Silicone additive B-6 Anti-tape (time) 9Solvent resistance more than 10

What is claimed is:
 1. A coating composition containing a nitrogenatom-containing organopolysiloxane represented by the average siloxaneunit formula (1):(R¹R²R³SiO_(1/2))_(a)(SiR¹ ₂O_(2/2))_(b)(R²R³SiO_(2/2))_(c)(R²R³₂SiO_(1/2))_(d)   (1) wherein R¹ is a nitrogen-free, substituted orunsubstituted, monovalent organic group of 1 to 20 carbon atoms, R³ isan organoxy group represented by —OR¹, “a” is a positive number of 0.7to 1.3; “b” is a positive number of 2 to 500; “c” is a positive numberof 0 to 10; “d” is a positive number 0.7 to 1.3; a+d is at least 2; andR² is a following general formula (2):—R⁴(NR⁵CH ₂CH₂)_(e)NR⁶ ₂   (2) wherein R⁴ is a divalent hydrocarbongroup of 1 to 6 atoms, R⁵ and R⁶ are independently selected fromhydrogen and unsubstituted or hydroxyl-substituted monovalenthydrocarbon groups of 1 to 50 carbon atoms which may be separated by anoxygen atom, and “e” is an integer of 0 to 4; and an organic polymerbinder.
 2. The coating composition of claim 1, wherein R² is —C₃H₆NH₂,—C₃H₆NHC₂H₄NH₂ or —C₃H₆NHC₂H₄NHC₂H₄NH₂.
 3. The coating composition ofclaim 1, wherein R³ is —OCH₃.
 4. The coating composition of claim 1,wherein “c” is
 0. 5. The coating composition of claim 1, wherein “b” isa number of 5 to
 100. 6. The coating composition of claim 1, wherein theorganic polymer binder is selected from the group comprising acrylicresin, polyurethane resin, epoxy resin, alkyd resin, polyamide resin,and the mixture of at least two of them.
 7. The coating composition ofclaim 1, wherein the composition further comprises a solvent.
 8. Thecoating composition of claim 1, wherein R² is —C₃H₆NHC₂H₄NH₂.
 9. Thecoating composition of claim 1, wherein R³ is —OC₂H₅.
 10. The coatingcomposition of claim 1, wherein “d” is
 1. 11. The coating composition ofclaim 1, wherein “b” is
 40. 12. A method for coating a surface of amaterial, wherein the surface material is coated with a coatingcomposition according to claim
 1. 13. A surface treated material with acoating composition according to claim
 1. 14. The coating composition ofclaim 1, wherein “a” is
 1. 15. The coating composition of claim 1,wherein R¹ is —CH₃.
 16. The coating composition of claim 1, wherein R²is —C₃H₆NHC₂H₄NHC₂H₄NH₂.
 17. The coating composition of claim 1, whereinR² is —C₃H₆NH₂.